This proposal details research for development of a new strategy for stereoselective synthesis of polyfunctional amines and application of this strategy to the total synthesis of amine-containing natural products. The strategy involves the use of electrophile-initiated cyclofunctionalization of unsaturated amine derivatives to effect relative asymmetric induction in the synthesis of both cyclic and acyclic systems. The target molecules selected have significant pharmacological and biological importance, and the methods to be developed would have the potential for application to many types of other pharmacologically important structures. Examples of natural product types to be investigated include polysubstituted piperidine and perhydropyridazine alkaloids and amino acids, novel polyfunctional amino acids for antibiotics and toxic mushrooms, and amino sugar constituents of antitumor antibiotics.